4-Substituted benzothiazol-2-ylazo-N-c8-14-alkykl-N-(2&#39;-cyanoethyl)anilines optionally having a 3-C1-4-alkyl group

ABSTRACT

Compounds of the formula   &lt;IMAGE&gt;   and mixtures thereof, wherien p1 R1 is hydrogen, chloro or bromo, p1 R2 is hydrogen, chloro, bromo or nitro, p1 R3 is hydrogen, chloro, bromo, nitro or -SCN, p1 R4 is hydrogen, chloro or bromo, p1 R5 is hydrogen or C1-4 alkyl, and p1 R5 is C8-14 alkyl, with the provisos that (i) at least one of R1, R2, R3 and R4 is other than hydrogen, (ii) when R3 is nitro or -SCN, R2 is other than nitro, and (iii) when two or more of R1, R2, R3 and R4 are halo, then R3 is one of those halos, are useful as disperse dyes for dyeing substrates such as synthetic and semi-synthetic, hydrophobic, high molecular weight organic materials.

This is a continuation-in-part of application Ser. No. 06/839,854, filedMar. 14, 1986 and now abandoned.

This invention relates to monoazo compounds suitable as disperse dyesfor dyeing substrates such as synthetic and semi-synthetic hydrophobichigh molecular weight organic materials.

According to the invention there is provided compounds of the formula##STR2## wherein

R₁ is hydrogen, chloro or bromo,

R₂ is hydrogen, chloro, bromo or nitro,

R₃ is hydrogen, chloro, bromo, nitro or --SCN,

R₄ is hydrogen, chloro or bromo,

R₅ is hydrogen or C₁₋₄ alkyl, and

R₆ is C₈₋₁₄ alkyl,

with the provisos that (i) at least one of R₁, R₂, R₃ and R₄ is otherthan hydrogen, (ii) when R₃ is nitro or --SCN, R₂ is other than nitro,and (iii) when two or more of R₁, R₂, R₃ and R₄ are halo, then R₃ is oneof those halos, and mixtures of such compounds.

Preferably, at least one of R₁, R₃ and R₄ is other than hydrogen.

Preferably, R₁ is hydrogen.

Preferably, R₅ is R₅ ', where R₅ ' is hydrogen, methyl or ethyl; morepreferably, it is R₅ ", where R₅ " is hydrogen or methyl.

Preferably, R₆ is R_(6a), where R_(6a) is n-C₁₀₋₁₄ alkyl; morepreferably, it is R₆ ', where R₆ ' is n-C₁₀₋₁₂ alkyl (i.e., linearC₁₀₋₁₂ alkyl).

Preferably when R₂ or R₃ is nitro, then R₆ is C₁₀₋₁₄ alkyl.

Preferred groups of compounds of formula I include those

(i) wherein one of R₂ and R₄ is chloro or bromo and the other ishydrogen, and R₃ is chloro or bromo,

(ii) of (i) wherein R₆ is n-C₁₀₋₁₂ alkyl,

(iii) of (ii) wherein one of R₂ and R₄ is chloro and the other ishydrogen, and R₃ is chloro,

(iv) of (iii) wherein R₁ is hydrogen,

(v) of (iv) wherein R₅ is hydrogen or methyl,

(vi) of (i) wherein (a) R₃ and R₂ or R₄ are both chloro or (b) R₃ and R₂or R₄ are both bromo,

(vii) of (vi) wherein R₁ is hydrogen,

(viii) of (vii) wherein R₆ is n-C₁₀₋₁₂ alkyl,

(ix) of (viii) wherein R₅ is hydrogen or methyl,

(x) wherein R₂ is nitro, R₃ is hydrogen, and R₄ is hydrogen,

(xi) of (x) wherein R₁ is hydrogen,

(xii) of (xi) wherein R₆ is n-dodecyl,

(xiii) of (xii) wherein R₅ is hydrogen or methyl,

(xiv) wherein R₂ is hydrogen, R₃ is nitro or --SCN, and R₄ is hydrogen,

(xv) of (xiv) wherein R₆ is n-dodecyl,

(xvi) of (xiv) wherein R₁ is hydrogen,

(xvii) of (xvi) wherein R₅ is hydrogen or methyl,

(xviii) of (xvii) wherein R₆ is n-C₁₀₋₁₂ alkyl,

(xix) of (xviii) wherein R₆ is n-dodecyl,

(xx)-(xxv) of (xiv)-(xix) wherein R₃ is nitro, and

(xxvi) of (xi) wherein R₅ is hydrogen or methyl.

Preferred groups of mixtures include mixtures of (xxvii)-(xxxv) twocompounds of any of (i)-(ix) that are identical except that in onecompound R₂ is chloro or bromo, and R₄ is hydrogen and in the other R₂is hydrogen, and R₄ chloro or bromo,

(xxxvi) two or three compounds of formula I that differ solely withrespect to R₆,

(xxxvii)-(xlv) four to six compounds of any of (i)-(ix) consisting oftwo or three pairs of compounds that are identical except that in onecompound of the pair R₂ is chloro or bromo, and R₄ is hydrogen and inthe other compound of the pair R₂ is hydrogen, and R₄ is chloro orbromo, the pairs of compounds differing from each other solely withrespect to R₆, and

(xlvi)-(lxiv) two or three compounds of any of (x), (xi), (xiv)-(xviii),(xx), (xxii), and (xxvi) that differ solely with respect to R₆.

In each of Groups (i), (vi), (vii), (x), (xi), (xiv), (xvi), (xvii),(xx), (xxiii), (xxvi), (xxvii), (xxxii), (xxxiii), (xxxvi), (xxxvii),(xlii), (xliii), (xlvi)-(l) and (lii)-(liv) each R₆ is preferably C₁₀₋₁₄alkyl and more preferably n-C₁₀₋₁₄ alkyl.

Except where indicated to the contrary, all alkyl groups are linear orbranched.

The compounds of formula I can be prepared by coupling a diazotisedamine of the formula ##STR3## to a compound of the formula ##STR4##

The mixtures may be prepared by mixing the individual components thereofor by utilizing in the aforementioned process a mixture of diazotisedamines of formula II and/or a mixture of compounds of formula III.

Compounds of formulae II and III are either known or may be preparedfrom appropriate compounds by known methods.

Diazotisation and coupling can be carried out by known methods.

The dyes according to the invention are in general applied to thesubstrate as dyeing preparations, by padding, printing or exhaustdyeing.

The formulation of the dyes according to the invention into dyeingpreparations can be carried out by known methods, e.g., by milling inthe presence of a dispersing agent or filler.

The dyes according to the invention exhaust well from a suspension attemperatures over 120° C. onto textile material made of fully syntheticor semi-synthetic hydrophobic, high molecular weight organic material.The dyes according to the invention are particularly useful for dyeing,padding or printing textile material comprising fibres of lineararomatic polyester.

Dyeing, padding or printing can be carried out according to knownmethods, for example as described in French Patent 1,445,371.

Dyeings made with dyes according to the invention have excellent wetfastness properties and excellent fastness to contact after thermaltreatment (e.g., after heat-setting with or without a finishing agent)and resin-finishing. Besides these good properties the dyeings exhibitother good fastness properties normally associated with disperse dyes.

The invention will now be illustrated by the following Examples in whichall parts and percentages are by weight and all temperatures are in °C.

EXAMPLE 1

11.5 Parts of a technical mixture of 2-amino-5,6-dichlorobenzothiazoleand 2-amino-6,7-dichlorobenzothiazole (95%) are dissolved in 23 parts ofglacial acetic acid, 2.5 parts of propionic acid and 41 parts of 85%phosphoric acid at 45°-50°. The solution is cooled to 0°-5° anddiazotised at this temperature with 17.5 parts of 40% nitrosylsulphuricacid and stirred for 3 hours. The resultant diazonium salt solution isslowly cooled to 0° C. and a solution of 14.9 parts ofN-β-cyanoethyl-N-decylaniline (96%) in 110 parts of glacial acetic acid,35 parts of water, 60 parts of ice and 3.5 parts of amidosulphonic acidis added. The resulting precipitate is a rubine-red dyestuff isfiltered, washed until acid-free and dried at 60° under vacuum. Thedyestuff can be purified by column chromatography (eluant:Toluene/methyl ethyl ketone) λmax of the purified compound in DMF is 522nm.

Modified Procedure

11.5 Parts of a technical mixture of 2-amino-5,6-dichlorobenzothiazoleand 2-amino-6,7-dichlorobenzothiazole (95%) are dissolved in a mixtureof 23 parts of glacial acetic acid, 2.5 parts of propionic acid and 41parts of 85% phosphoric acid at 45°-50° C. The solution is cooled to-5°-0° C., diazotised at this temperature with 16.7 parts of 40%nitrosylsulphuric acid and stirred for 3 hours. A solution of 14.9 partsN-β-cyanoethyl-N-decylaniline (96%), 1.2 parts of an emulsifier (e.g.,an emulsifier consisting of, by weight, 99.7% of the reaction product ofcastor oil and ethylene oxide containing an average of 32 ethylene oxideunits per molecule and 0.3% of sodium chloride) and 0.5 part ofamidosulphonic acid in 22 parts of glacial acetic acid is made up at25°-30° C. To this solution the diazonium salt solution and 80 parts ofice cold water are added simultaneously. The resulting precipitate is arubine red dye. It is isolated and may be purified as set forth in thepreceding paragraph.

EXAMPLES 2-8

Mixtures of compounds of the formula ##STR5##

in which R₅ and x are as defined in the Table 1 below can be made by amethod analogous to that of Example 1 from the same diazo component andappropriate coupling components.

                  TABLE 1                                                         ______________________________________                                        Ex. No.      R.sub.5    x     λ.sup.max .sub.in nm                     ______________________________________                                        2            H          10    522                                             3            H          11    522                                             4            H          13    522                                             5            --CH.sub.3 9     529                                             6            --CH.sub.3 10    529                                             7            --CH.sub.3 11    529                                             8            --CH.sub.3 13    529                                             ______________________________________                                    

EXAMPLES 9-13

Mixtures of compounds of the formula ##STR6##

in which R₅, x and the ratio of compounds are given in Table 2 below,can be made by a method analogous to that of Example 1 from the samediazo component and suitable coupling components.

                  TABLE 2                                                         ______________________________________                                                                  Ratio of compounds                                  Ex. No. R.sub.5    x      %            max                                    ______________________________________                                                  H             9    85                                               9                                        522                                          H              11   15                                                        H              8    20           522                                  10      H              9    60                                                        H              11   20                                                                  9     70   522                                              11                                                                                    H              11   30                                                         --CH.sub.3     9    70           529                                 12                                                                                    --CH.sub.3     11   30                                                         --CH.sub.3     9    9            529                                 13                                                                                    --CH.sub.3     11   15                                                ______________________________________                                    

EXAMPLES 14-16

In a method analogous to that of Example 1 compounds can be preparedfrom the following diazo and coupling components.

In Examples 14 and 15 the diazo component is a technical mixture of2-amino-5,6-dibromobenzothiazolyl-2 and2-amino-6,7-dibromobenzothiazolyl-2 and in Example 16 the diazocomponent is the technical mixture of Example 1. The coupling componentsare given in Table 3 below together with the λmax of the resultingdyestuffs.

                  TABLE 3                                                         ______________________________________                                        Ex.                                                                           No.   Coupling component      λ max in nm                              ______________________________________                                        14    Nβ-cyanoethyl-Ndecylaniline                                                                      522                                             15    Nβ-cyanoethyl-Ndecyl- .sub.--m-toluidine                                                         529                                             16                                                                                   ##STR7##               522                                             ______________________________________                                    

The arrow in the above table indicates where coupling occurs.

EXAMPLE 17

Into a mixture of 150 parts of 85% phosphoric acid, 90 parts of glacialacetic acid and 8.5 parts of propionic acid, 20.1 parts of2-amino-6-nitrobenzothiazole (97%) are dissolved at 50°-55° and thesolution, after cooling to -5°, is diazotised with 35 parts ofnitrosylsulphuric acid (40%). The resulting brown solution is thendiluted with 160 parts of water and at the same time a solution,consisting of 31 parts N-dodecyl-N-(2'-cyanoethyl)aminobenzene (100%)(in the form of 35 parts of about 88% compound), 170 parts of glacialacetic acid, 2 parts of a commercially available surfactant (thereaction product of 32 moles of ethylene oxide and 1 mole of castor oil)and 0.5 parts of aminosulphonic acid, is added whilst stirring well at20° to 30°.

The resulting dyestuff is filtered, washed neutral with water at 80° andvacuum dried at 50°.

The impure dyestuff (circa 85%) can be purified by recrystallisation orcolumn chromatography (eluant: toluene/ethyl methyl ketone).

A compound of formula 17a ##STR8## results; it dyes polyester andPES/cellulose fibre material a clear bordeaux red colour. The dyeingshave excellent wet fastness properties.

EXAMPLES 18-28

Compounds of the formula ##STR9## in which the symbols are defined inTable 4 below can be prepared from appropriate reactants by a methodanalogous to that of Example 17 above.

                                      TABLE 4                                     __________________________________________________________________________    Ex.                      Nuance of                                                                             max                                          No.                                                                              R.sub.2                                                                           R.sub.3                                                                            R.sub.5                                                                             R.sub.6                                                                              dyeing on PES                                                                         in nm                                        __________________________________________________________________________    18 H   --NO.sub.2                                                                         H     --C.sub.11 H.sub.23                                                                  bluish-red                                                                            543                                          19 H   --NO.sub.2                                                                         H     --C.sub.14 H.sub.29                                                                  bluish-red                                                                            543                                          20 H   --NO.sub.2                                                                         CH.sub.3                                                                            --C.sub.12 H.sub.25                                                                  reddish-violet                                                                        551                                          21 --NO.sub.2                                                                        H    H     --C.sub.11 H.sub.23                                                                  yellowish-red                                                                         520                                          22 --NO.sub.2                                                                        H    H     --C.sub.12 H.sub.25                                                                  yellowish-red                                                                         520                                          23 --NO.sub.2                                                                        H    --CH.sub.3                                                                          --C.sub.12 H.sub.25                                                                  red     528                                          24 H   --SCN                                                                              H     --C.sub.10 H.sub.21                                                                  yellowish-red                                                                         521                                          25 H   --SCN                                                                              H     --C.sub.11 H.sub.23                                                                  yellowish-red                                                                         521                                          26 H   --SCN                                                                              H     --C.sub.12 H.sub.25                                                                  yellowish-red                                                                         521                                          27 H   --SCN                                                                              --CH.sub.3                                                                          --C.sub.12 H.sub.25                                                                  red     529                                                            1:2 mixture                                                                          bluish-red                                                                            543                                                            of                                                          28 H    --NO.sub.2                                                                        H     --C.sub.11 H.sub.23 and                                                       --C.sub.12 H.sub.25                                         __________________________________________________________________________

APPLICATION EXAMPLE

The dyestuff produced according to Example 1 is sandmilled in thepresence of a dispersing agent (e.g., a commercially availablelignosulphonate) and is then atomised to form an ultradispersepreparation having an average particle size of 1μ and a dyestuff/coupageratio of 3.5:10.

24 Parts of this preparation are dispersed in 1000 parts of water andare added to a circulating liquor (13,000 parts containing 30 partsammonium sulphate, 0.3 parts of formic acid as buffer, 13 parts ofsulphonated castor oil and optionally a carrier/levelling combination)of a dyeing autoclave at 60°.

A pre-cleaned, pressed crosswound spool (1000 parts of polyester yarn ona plastic spool) is immersed to the bath and the dyeing autoclave isclosed and heated over 35 minutes to 130° to 135°. After 90 minutes thetemperature is reduced to 80° and the circulating liquor is removed. Thedyed substrate is thoroughly washed with cold water and then reductivelycleared. The substrate is then rinsed and then dried. The resultantdyeing is a deep, level scarlet-red dyeing free of residues.

Instead of using the compound of Example 1, an appropriate amount of thecompound of any one of Examples 2-28 may be used instead.

The decyl groups in Examples 1, 14 and 15 are linear.

The C₁₀₋₁₄ alkyl groups of Examples 17-28 are linear.

What is claimed is:
 1. A compound of the formula ##STR10## or a mixturethereof, wherein R₁ is hydrogen, chloro or bromo,R₂ is hydrogen, chloro,bromo or nitro, R₃ is hydrogen, chloro or bromo, R₄ is hydrogen, chloroor bromo, R₅ is hydrogen or C₁₋₄ alkyl, and R₆ is C₁₀₋₁₄ alkyl,withprovisos that (i) at least one of R₁, R₂, R₃ and R₄ is other thanhydrogen, and (ii) when two or more of R₁, R₂, R₃ and R₄ are halo, thenR₃ is one of those halos.
 2. A compound according to claim
 1. 3. Acompound according to claim 1, or a mixture thereof, wherein R₁ ishydrogen.
 4. A compound according to claim 1, or a mixture thereof,wherein R₅ is hydrogen, methyl or ethyl.
 5. A compound according toclaim 4, or a mixture thereof, wherein R₅ is hydrogen or methyl.
 6. Acompound according to claim 1, or a mixture thereof, wherein R₆ isn-C₁₀₋₁₂ alkyl.
 7. A compound according to claim 1 whereinR₂ is nitro,R₃ is hydrogen, and R₄ is hydrogen.
 8. A compound according to claim 7whereinR₁ is hydrogen, R₅ is hydrogen or methyl, and R₆ is n-dodecyl. 9.A substrate to which a compound according to claim 1, or a mixturethereof, has been applied.
 10. A compound of the formula ##STR11##wherein R₅ is hydrogen or C₁₋₄ alkyl, andR₆ is C₁₀₋₁₄ alkyl.
 11. Acompound according to claim 10 wherein R₅ is hydrogen or methyl.
 12. Acompound according to claim 11 wherein R₆ is n-C₁₀₋₁₂ alkyl.
 13. Acompound of the formula ##STR12## or a mixture thereof, wherein R₁ ishydrogen, chloro or bromo,one of R₂ and R₄ is chloro or bromo and theother is hydrogen, R₃ is chloro or bromo, R₅ is hydrogen or C₁₋₄ alkyl,and R₆ is C₈₋₁₄ alkyl.
 14. A compound according to claim 13, or amixture thereof, wherein R₆ is n-C₁₀₋₁₂ alkyl.
 15. A compound accordingto claim 14, or a mixture thereof, whereinR₁ is hydrogen, R₃ and R₂ orR₄ are both chloro or R₃ and R₂ or R₄ are both bromo, and R₅ is hydrogenor methyl.
 16. A compound according to claim
 15. 17. A mixture accordingto claim 15, said mixture consisting essentially of two compounds thatare identical except that in one compound R₂ is chloro or bromo, and R₄is hydrogen and in the other R₂ is hydrogen, and R₄ is chloro or bromo.18. A mixture according to claim 17 consisting essentially of the twocompounds of the formula ##STR13##
 19. A mixture according to claim 17consisting essentially of the two compounds of the formula ##STR14##